Photographic materials and processes for developing photographic compositions having a zwitterionic and anionic elements

ABSTRACT

PHOTOGRAPHIC COMPOSITIONS AND ELEMENTS COMPRISING A ZWITTERIONIC COMPOUND AND AN ANIONIC COMPOUND. IN ONE ASPECT, THIS INVENTION RELATES TO A PROCESS COMPRISING DEVELOPING A PHOTOGRAPHIC IMAGE IN THE PRESENCE OF A ZWITTERIONIC COMPOUNDAND AN ANIONIC COMPOUND. IN ANOTHER ASPCT, THIS INVENTION RELATES TO A PHOTOGRAPHIC DEVELOPER COMPOSITION COMPRISING A PHOTOGRAPHIC DEVELOPING AGENT, A SWITTERIONIC COMPOUND, AND AN ANIONIC COMPOUND.

United States Patent 3,573,049 PHOTOGRAPHIC MATERIALS AND PROCESSES FORDEVELOPING PHOTOGRAPHIC COMPOSI- TIONS HAVING A ZWITTERIONIC AND ANHONICELEMENTS Norman W. Kalenda, Rochester, N.Y., assignor to Eastman KodakCompany, Rochester, N.Y. No Drawing. Filed Oct. 2, 1967, Ser. No.671,955 Int. Cl. G03c 5/30 US. Cl. 96-663 20 Claims ABSTRACT OF THEDISCLOSURE Photographic compositions and elements comprising azwitterionic compound and an anionic compound. In one aspect, thisinvention relates to a process comprising developing a photographicimage in the presence of a zwitterionic compound and an anioniccompound. In another aspect, this invention relates to a photographicdeveloper composition comprising a photographic developing agent, azwitterionic compound, and an anionic compound.

This invention relates to novel photographic materials and theirpreparation and to novel photographic processes. In one aspect, thisinvention relates to a means for reducing fog in photographic emulsionsand elements which contain a zwitterionic compound. In another aspect,this invention relates to photographic emulsions, elements and processesin which zwitterionic compounds are used in combination with anioniccompounds.

It is known to use certain zwitterionic compounds as wetting agents toproduce photographic emulsions having improved wetting characteristics.In US. Pat. 2,197,809 of McQueen, granted Apr. 23, 1940, variouscation-active surface active compounds including certain betaines areincorporated in photographic emulsions to give more thorough wetting ofthe emulsion during development. Zwitterionic compounds have also beenused as coating aids. In U.S. Pat. 3,133,816 of Ben-Ezra, granted May19, 1964, certain betaines are used in combination with certain aminoacids as a coating solution for photographic materials. However, many ofthese zwitterionic surfactants strongly increase development fog andtend to produce high fog on storage.

Thus, it is an object of this invention to provide new photographiccompositions.

Another object of this invention is to provide novel photographicemulsions and elements which comprise a zwitterionic compound and whichhave reduced fog on development and incubation.

A further object of this invention is to provide photographic emulsionsand elements which have improved wettability.

Still another object of this invention is to provide photographicemulsions and elements which have lower surface resistivity.

Another object of this invention is to provide novel developercompositions and novel processes for developing photographic emulsionsand elements which result in reduced fogging.

Other objects will be apparent from the specification and claims.

It has been found that these and other objects are accomplished by usinga zwitterionic compound in combination with an anionic compound inphotographic emulsions, elements and processes. The use of the anioniccompound with the zwitterionic compound makes it possible to obtain theadvantages of the zwitterionic compounds in photographic applicationswithout the increases in fog often associated with the use of theZwitterions 3,573,049 Patented Mar. 30, 1971 alone. The Zwitterions andanions of the invention can be contained in a photographic emulsion orelement, as well as in a processing solution or element, and can becombined individually or together with a photographic developing agentin a photographic developer composition. The zwitterionic compound andthe anionic compound can be contained in the same or in different layersin a photographic element.

The zwitterionic compounds employed in the practice of this inventionare compounds which contain both a negatively and a positively chargedatom in each molecule. Zwitterions are also sometimes referred to asinner salts. These Zwitterions can be represented generically ascompounds having the formula C BA wherein C represents an organiccationic residue and BA repre sents the covalently bound anionic part ofthe molecule in which A can be an anionic acid residue such as, forexample, carboxylate (--CO sulfonate (SO sulfate (-OSO and the like. TheZwitterions can be used in the form of adducts with protonic acids.

Typical zwitterionic compounds which are useful in this inventioninclude betaines such as:

( IO-carboxydecyl) dimethyldodecylammonium hydroxide, inner salt,

(Z-carboxy-i-butyl dimethyldodecylammonium hydroxide, inner salt,

(2-carb oxyethyl) dimethyldodecylammonium hydroxide, inner salt,

(2-carb oxymethyl) dimethyldodecylammonium hydroxide, inner salt,

(3-sulfopropyl)dimethyldodecylamrnonium hydroxide, inner salt,

(4-sulfobutyl)dimethyldodecylammonium hydroxide, inner salt,

(3-sulfobutyl) dimethyldodecylammonium hydroxide, inner salt,

(3 -sulfopropyl) diethyldodecylammonium hydroxide, inner salt,

(4-sulfobutyl) diethyldodecylammonium hydroxide, inner salt,

( 2-carboxyethyl) dimethyloctadecylammonium hydroxide, inner salt,

(carboxymethyl) dimethyloctadecylamrnonium hydroxide, inner salt,

(3-sulfopropyl)dimethyloctadecylammonium hydroxide, inner salt,

pyridinium betaines, such as:

1-(l-carboxytridecyl)pyridinium hydroxide, inner salt,1-(l-carboxyundecyl)pyridinium hydroxide, inner salt,1-(10-carboxydecyl)pyridinium hydroxide, inner salt,1-(10-sulfatodecyl)pyridinium hydroxide, inner salt,3-carbethoxy-1-(10-carboxydecyl)pyridinium hydroxide, inner salt,l-(17-carboxy-6-oxo-7-azaheptadecyl)pyridinium hydroxide, inner salt,3-carboxy-l-dodecylpyridinium hydroxide, inner salt,

thetins, such as:

( l-carboxyethyl) methyldodecylsulfonium hydroxide,

inner salt,

(Z-carboxyethyl)methyldodecylsulfonium hydroxide,

inner salt,

(3-sulfopropyl)methyldodecylsulfonium hydroxide,

inner salt,

(2-carboxyethyl)methylhexadecylsulfonium hydroxide,

inner salt,

( l-carboxyethyl)methylhexadecylsulfonium hydroxide,

inner salt,

(2-carboxy-i-butyl)methyldodecylsulfonium hydroxide,

inner salt,

3 10-carboxydecyl tetrahydrothiophenium hydroxide,

inner salt,

and the like.

A preferred class of zwitterionic compounds useful in the practice ofthis invention are the sulfobetaines. Sulfobetaines are zwitterioniccompounds which have a positively charged nitrogen atom and have asulfonate group (-80 in the covalently bound anionic part of themolecule. Sulfobetaines can be generally represented by the followingformula:

wherein R R and R can be unsubstituted or substituted alkyl or arylgroups, such as methyl, ethyl, propyl, 2- methylpropyl, decyl,hexadecyl, hydroxyethyl, benzyl, and the like, and phenyl, naphthyl,tolyl and the like; and two or more of the groups R R or R can be takentogether to form a heterocyclic ring having one or more hetero atoms; R,is an unsubstituted or substituted alkyl chain containing one or morecarbon atoms, such as a methyl, ethyl, pentyl, Z-methylpropyl and decylchain and the like.

Typical sulfobetaines useful in this invention include:

(3-sulfopropyl) dimethyldodecylammonium hydroxide,

inner salt,

(4-sulfobutyl) dimethyldodecylammonium hydroxide,

inner salt,

(3-sulfobutyl) dimethyldodecylammonium hydroxide,

inner salt,

(3-sulfopropyl diethyldodecylammonium hydroxide,

inner salt,

(4-sulfobutyl)diethyldodecylammonium hydroxide,

inner salt,

(3-sulfopropyl dimethylo ctadecylammonium hydroxide, inner salt,

and the like.

Sulfobetaines are generally prepared by reacting a tertiary amine with asulfone or by quaternizing a tertiary aminoalkylene sulfonate. Forexample,

SOaR

l SOa a carboxylate (CO and the like. In one embodiment, these acidicsubstituents can be contained in monomers which are reacted to form apolymer or can be added to a polymeric molecule during or after thepolymerization reaction. In one preferred embodiment, the anionic acidicsubstituent is a sulfoxy substituent, a radical which has at least onesulfur atom and at least one oxygen atom and which has a net negativecharge. Typical anionic compounds which are useful in the inventioninclude polyalkylene glycol ether sulfates, poly(sulfoalkylacrylates),for example, such as those disclosed in Belgian Pat. 679,412 issued Oct.12, 1966, carboxylated fatty alcohols and the like. In a preferredembodiment of the invention the zwitterionic compound is(3-sulfopropyl)dimethyldodecylammonium hydroxide, inner salt, and theanionic compound is the ammonium salt of dodecyl phenyl polyethyleneglycol ether sulfate or copoly(butyl acrylatesulfopropyl acrylate).

In one embodiment, when the anionic compounds such as, for example,polyethylene glycol ether sulfates are used with the sulfobetaines suchas (3-sulfopropyl)dimethyldodecyl ammonium hydroxide, inner salt,processed coatings having higher wettability and unprocessed coatingshaving lower surface resistivity are obtained as r well as a reductionin fogging. Higher wettability reduces the tendency of water dropletformation on the surface of the emulsion thus reducing water spottingduring drying of the emulsion. Lower surface resistivity will diminishproblems resulting from static electricity in the film such asincidental visible electrical discharges which leave latent images inthe photographic emulsion.

In a preferred embodiment of this invention, the photographic elementscontain silver halide emulsions. The silver halide, the zwitterioniccompound and the anionic compound can be contained in the same layer orin different layers of a photographic element. The preferredconcentration of the zwitterions in the silver halide emulsions and inelements of the invention is from about 0.50 to 50 grams per mole ofsilver in the silver halide layer and is generally from about 1.0 to 30grams per mole of silver in the silver halide layer. The preferredconcentration of the anionic compound in the silver halide emulsions andelements of the invention is from about 5 milligrams to 25 grams permole of silver in the silver halide layer, and is generally from about0.1 to 10 grams per mole of silver in the silver halide layer.

Any suitable photographic developing agent can be used in the developercompositions of this invention. Typical developers includepolyhydroxybenzenes such as hydroquinone, pyrogallol, catechol, and thelike, ascorbic acids, 3-pyrazolidones, p-aminophenols,phenylenediamines, and the like. The developer compositions of theinvention comprise a photographic developing agent and generally fromabout 1.0 to 50 grams per liter of the developer composition of azwitterionic compound and from about 50 milligrams to 25 grams per literof the developer composition of an anionic compound. Furthermore, thezwitterionic compound can be contained in an emulsion while the anioniccompound is in a processing solution or element, and similarly the anioncan be contained in an emulsion while the zwitterion is in a processingsolution or element.

The new developer compositions according to this invention can beprovided in kit form as long as the essential ingredients are present,namely the developer, the zwitterionic compound and/or the anioniccompound. The kit may comprise diluted, concentrated or powdered formsof said ingredients individually packaged or combined together, whichcan be used to form an aqueous bath of said ingredients. The compoundsare generally provided individually in a form which can be added towater just prior to using the developer bath.

The emulsion can also contain additional additives, particularly thoseknown to be beneficial in photographic emulsions, including for example,stabilizers or antifog gants, particularly the water-soluble inorganicacid salts of cadmium, cobalt, manganese and zinc as disclosed in U.S.Pat. 2,829,404, the substituted triazaindolizines as disclosed in U.S.Pats. 2,444,605 and 2,444,607, speed increasing materials, absorbingdyes, plasticizers and the like. Suitable hardeners which can be usedinclude, for example, formaldehyde, mucochloric acid, glutaraldehydebis(sodium bisulfite), maleic dialdehyde, aziridines, dioxanederivatives and oxypolysaccharides. Sensitizing dyes useful insensitizing such emulsions are described, for example, in U.S. Pats.2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 ofSprague issued Apr. 11, 1950. Sensitizers which give particularly goodresults in the photographic compositions disclosed herein are thealkylene oxide polymers which can be employed alone or in combinationwith other materials, such as quaternary ammonium salts, as disclosed inU.S. Pat. 2,886,437 or with mercury compounds and nitrogen containingcompounds as disclosed in U.S. Pat. 2,751,299. Spectral sensitizerswhich can be used are the cyanines, merocyanines, complex (trinuclear)cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.

Various silver salts can be used as the sensitive salt such as silverbromide, silver iodide, silver chloride, or mixed silver halides such assilver chlorobromide or silver bromoiodide. The silver halidespreferably used can be those which form latent images predominantly onthe surface of the silver halide grains or those which form latentimages inside the silver halide crystals such as described in U.S. Pat.2,592,250 of Davey and Knott issued Apr. 8, 1952. Particularly usefulare high contrast photographic emulsions of the type described in U.S.Pat. 2,756,148 of MacWilliams, granted July 24, 1956.

The silver halide emulsion layer of a photographic element which isuseful in the instant invention can contain any of the hydrophilic,water permeable binding materials suitable for this purpose. Suitablematerials include gelatin, colloidal albumin, polyvinyl compounds,cellulose derivatives, acrylamide polymers, etc. Mixtures of thesebinding agents can also be used. The binding agents for the emulsionlayer of the photographic element can also contain dispersed polymerizedvinyl compounds. Such compounds are disclosed, for example, in U.S.Pats. 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of Whiteissued July 6, 1965; 3,062,674 of Houck et al. issued Nov. 6, 1962 and3,220,844 of Houck et al. issued Nov. 30, 1965; and include the waterinsoluble polymers of alkyl aerylates and methacrylates, acrylic acid,sulfoalkyl acrylates or methacrylates and the like.

emulsions useful in the instant invention can be further enhanced byincluding in the emulsions a variety of hydrophilic colloids such ascarboxymethyl protein of the type described in U.S. Pat. 3,011,890 ofGates, Jr., et al. issued Dec. 5, 1961, and polysaccharides of the typedescribed in Canadian Pat. 635,206 of Koller et al. issued Jan. 23,1962.

The photographic elements prepared according to the instant inventioncan be used in various kinds of photographic systems. In addition tobeing useful in X-ray and other nonoptically sensitized systems, theycan also be used in orthochromatic, panchromatic and infrared sensitivesystems. The sensitizing addenda can be added to photographic systemsbefore or after any sensitizing dyes which are used.

Silver halide emulsions useful in the instant invention can besensitized using any of the well known techniques in emulsion making,for example, by digesting with naturally active gelatin or varioussulfur, selenium, tellurium compounds and/ or gold compounds. Theemulsions can also be sensitized with salts of noble metals of GroupVIII of the Periodic Table which have an atomic weight greater than 100.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated.

EXAMPLE 1 A large grain silver bromoiodide emulsion having 473 mg. ofsilver per square foot and 350 mg. of gelatin per square foot and agelatin overcoat having 130 mg. of gelatin per square foot are coatedonto a poly(ethylene terephthalate) support. The anionic compounds ofTable I and the zwitterion (3-sulfopropyl)dimethyldodecylammoniumhydroxide, inner salt, are each coated in a gelatin overcoat at 7.5 mg.per square foot. The coatings are exposed on an Eastman IB Sensitometerand developed for six minutes in an Elon-hydroquinone developer.

Wettability is determined by measuring the surface area of the emulsioncovered by one milliliter of distilled water.

Using the following anionic compounds:

(A) ammonium salt of dodecylphenylpolyethylene glycol ether sulfate, and(B) copoly (butylacrylate-sulfopropylacrylate the following results wereobtained:

The silver halide emulsion of a photographic element which is useful inthe instant invention can be coated on a wide variety of supports.Typical supports are cellulose nitrate film, cellulose ester film,polyvinyl acetal film, polystyrene film, polyester film supports such aspoly- (ethylene terephthalate) and related films or resinous materialsas well as glass, paper, metal and the like. Supports such as paperwhich are coated with u-olefin polymers, particularly polymers ofu-olefins containing two or more carbon atoms, as exemplified bypolyethylene, polypropylene, ethylenebutene copolymers and the like canalso be employed.

The sensitometric characteristics of the photographicpropyl)dimethyloctadecylammonium hydroxide, inner salt, (l-carboxyethyl)methyldodecylsulfonium hydroxide, inner salt, and(4-sulfobutyl)dimethyldodecylammoninum hydroxide, inner salt, are testedin the same manner, similar results are obtained. Similar results arealso obtained when the zwitterionic compounds and anionic compounds areused in the developing composition.

The invention has been described in considerable detail with referenceto preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention as described hereinabove and as defined in the appendedclaims.

I claim:

1. A photographic element comprising (1) a support, (2) at least onelayer coated thereon containing a photographic silver halidecomposition, (3) at least one layer coated thereon which contains azwitterionic compound and (4) at least one layer coated thereon whichcontains at least 5 milligrams of anionic surfactant per mole of silverin said layer containing silver halide.

2. A photographic element according to claim 1 wherein said layercontaining silver halide comprises at least 0.50 gram of saidzwitterionic compound per mole of silver and at least 5 milligrams of ananionic surfactant per mole of silver.

3. A photographic element according to claim 1 wherein said anionicsurfactant has at least one anionic acid substituent.

4. A photographic element according to claim 3 wherein said anionicsubstituent is a sulfate group, a sulfonate group or a sulfoxylategroup.

5. A photographic element according to claim 1 wherein said layercontaining silver halide further comprises gelatin.

6. A photographic element according to claim 1 wherein said zwitterioniccompound is a sulfobetaine.

7. A photographic element according to claim 1 wherein said zwitterioniccompound is (3-sulfopropyl)dimethyldodecylammonium hydroxide, innersalt.

8. A photographic element according to claim 1 wherein said anionicsurfactant is a polyalkylene glycol ether sulfate.

9. A photographic element according to claim 1 wherein said anionicsurfactant is a poly(sulfoalkylacrylate).

10. A photographic element according to claim 1 wherein saidzwitterionic compound is (sulfopropyl)din1ethyldodecylammoniumhydroxide, inner salt, and said anionic surfactant is the ammonium saltof dodecylphenylpolyethylene glycol ether sulfate.

11. A photographic element according to claim 1 where- 8 in saidzwitterionic compound is (3-sulfopropyl)dimethyldodecylammoniumhydroxide, inner salt, and said anionic surfactant iscopoly(butylacrylate-sulfopropyl acrylate).

12. A photographic composition comprising a gelatinous, light-sensitive,silver halide emulsion, at least 0.50 gram per mole of silver of azwitterionic surfactant and at least 5 milligrams of an anionicsurfactant per mole of silver.

13. A photographic composition according to claim 12 wherein saidanionic surfactant comprises sulfate groups, sulfonate groups orsulfoxylate groups.

14. A photographic composition according to claim 12 wherein saidzwitterionic surfactant is a sulfobetaine compound.

15. In a process for producing an image in a photographic elementcontaining at least one layer which comprises a silver halidecomposition, the improvement comprising developing said silver halidecomposition in the presence of a zwitterionic compound and an anionicsurfactant.

16. A process according to claim 15 wherein said zwitterionic compoundis a sulfobetaine and said anionic surfactant contains sulfate groups,sulfonate groups or sulfoxylate groups.

17. A photographic developer composition comprising a silver halidedeveloping agent, at least about 1.0 gram per liter of a zwitterioniccompound and at least about milligrams per liter of an anionicsurfactant.

18. The developer composition of claim 17 wherein said zwitterioniccompound is a sulfobetaine.

19. The process of claim 17 wherein said anionic surfactant is a polymerhaving at least one anionic acidic substituent.

20. A kit comprising the ingredients for providing said composition ofclaim 17.

References Cited UNITED STATES PATENTS 2,719,087 9/1955 Knox et al.96114.5 2,922,690 1/ 1960 Mueller et al. 8-21 3,113,026 12/1963 Sprung96107 OTHER REFERENCES Moilliet, J. L.: Surface Activity, Van Nostrand,1961.

NORMAN G. TORCHIN, Primary Examiner J. L. GOODROW, Assistant ExaminerUS. Cl. X.R. 96114.5

